Solidified normally liquid hydrocarbons



Patented Sept. 2

uni ran stares PATENT sonmrrmn NOBMALLY mourn nrnaocaanous Albert Joseph Laliberte, Naugatuck, Com, as-

signor to Safety-Fuel Incorporated, West Cheshire, Conn, a corporation of Connecticut No Drawing. Application March 18, Serial No. 435,168

3-Claims.

This invention relates to new and useful improvements in solidified normally liquid hydrocarbons.

The normally liquid hydrocarbon herein referred to are of the inflammable type and are preferentially of the combustible fuel type. One example is, for instance, a petroleum distillate. Another example is a mixture of hydrocarbons of the benzene series. Although such normally liquid hydrocarbons as are used for fuel ordinarily contain numerous hydrocarbons, the term hydrocarbons as used herein includes the limitlng case in which only one hydrocarbon is present. As a normally liquid hydrocarbon, for instance, gasoline may be used, although a petroleum distillate of closer boiling point is preferred. Also benzol or a light coal tar distillate consist- Depending upon the reactants used. the tempering predominantly of benzol homologues may be used. The normally liquid hydrocarbons herein mentioned are preferably for ordinary use readily inflammable and preferentially then possess a flash point not substantially above normal temperature so that combustion may be started by means of a match or similar lighter while the fuel is at normal temperature.

One method of solidifying normally liquid hydrocarbons comprises the formation, in situ, in the hydrocarbon to be solidified of a voluminous gel of a metallic soap substantially insolubleor limitedly soluble in said hydrocarbon. This is accomplished by reactinga hydrocarbon solution of a, suitable organic compound, saponifiable to yield a voluminous metallic soap, with a suitable saponification agent suspended in the hydrocarbon solution in substantially dry pulverulent form, and permitting the reaction to proceed in at least the last stages thereof while the reaction mix is in substantially quiescent condition.

The saponiflcation reaction is preferably one of acid neutralization. The suspension of saponification agent must be maintained substantially stable during at least the quiescent stage of the reaction, 1. e., no appreciable segregation of 'suspended particles should occur u on discontinuance of agitation This may be accomplished by the formation of a portion of the soap gel to a point at which the'viscosity imparted to the mix by the gel is sufiicient to substantially maintain the particles in suspension while themix is quiescent and in the limiting case by a suspension of particles of saponiflcation agent oi such fineness that the same remain suspended substantially without presence of soap gel. In any case, however, viscosity of the mix and particle size of saponificatlon agent must be so coordinated at ature requirements mayvary. Insome cases a temperature of about 40 C. may suffice while in other cases materially higher temperatures must be resorted to. The reaction mix is agitated and preferably substantially maintained at that temperature until gel formation has proceeded to a point at which the desired viscosity is obtained. Heating and agitation may then be discontinued and the reaction will proceed while the mix is substantially quiescent at a more or less rapid pace. Completion of the solidification while the mix is substantially quiescent is of importance as disturbance by agitation during at least the last stages ofcongelation is detrimental to the desired characteristics and particularly to the homogeneity of the solidified product.

In certain instances the saponification reaction requires agitation to almost the point of completion so that the resulting product is more or less lacking in the desired degree ofh'omogeneity necessary for a satisfactory solidified product. This is particularly the case when the suspension of saponiflcation agent is not sufllciently fine to be kept in suspension by the viscosity imparted to the hydrocarbon solution with the first gel formation or where the reaction between initial and final gel formation proceeds so rapidly that no satisfactorily quiescent state can be achieved for the ultimate congelation. Alternatively, the agitation may have been carried for other reasons or even inadvertently by oversight too far to permit quiescent last stage solidification.

I have discovered that from the granular product of unsatisfactory homogeneity a satisfactory solidified material may be obtained by the use of a relatively small amount of alcohol.

In accordance with the invention, the granular soap gel is heated slightly in the presence of a relatively small amount of alcohol and thereupon left quiescent to cool. The heating is carried out at such temperature and for such time as will serve to procure a saturated solution of the soap gel in the amount of alcohol present. Upon cooling the thus precipitated soap gel will act as a, cementitious agent cementing together the soap gel granules to form a solidified product of a high degree of homogeneity.

The alcohol used in accordance with the invention is preferably of the water soluble aliphatic type and should as such constitute at least limitedly a solvent for the metallic soap constituting the voluminous gel in the solidified hydrocarbon product. When alcohol has been introduced for instance by way of ,the saponification agent, as for example, when using alcoholates, or has been added by way of reaction booster, the same may sufilce to produce the desired efiect.

of the granular particles, by way of heating the same in the presence of alcohol, it is possible to add a small amount of a hot separately prepared more or less saturated soap solution and have the entire mass thereupon congeal quiescent upon cooling. In any case, however the hot granular gel should be permitted to cool in the pres- I ence of the alcohol.

The procedure in accordance with the invention is, for instance, exemplified in the following example:

Example A granular solidified hydrocarbon product of unsatisfactory homogeneity and comprising subcarbon solution of the aliphatic acid, or by first preparing a fine dispersion of such saponification agent in substantially dry form in a part of the total hydrocarbon ultimately to be solidified and adding such dispersion to the other part of such hydrocarbon in which the aliphatic'acid has been dissolved. It is also sometimes of advantage and desirable to initiate or expedite the saponification reaction by passing the reaction mix through a colloid mill or other device for procuring finest dispersion. Such dispersion device may be also of advantage to procure finest dispersion in the case where a preliminary dispersion of th saponification agent in a hydrocarbon solution is used.

When using alcoholates they are preferably the I methyl alcohol, ethyl alcohol and the like, alcostantially a solid system with about 6% sodium resinate and about 94% hydrocarbon of a boiling range of 145 to 210? F. was heated to about 125.F. in the presence of 1.0% of methyl alcohol for about 5 to 10 minutes. The mix was then permitted to cool while quiescent and a solidified product of satisfactory homogeneity was obtained. Instead of a product containing. sodium resinate other granular products of unsatisfactory homogeneity such as those containing sodium stearate or a mixture of sodium stearate and sodium resinate may be substituted in the following procedure of the foregoing example.

The organic compound herein referred to is preferably an organic acid of the rosin acid, or

varying proportions. Commercial products of this type are, for instance, coconut oil fatty acids,

- peanut oil fatty acids, palm oil fatty acids and the like. For best results rosin or stearic acid or amixture thereof may be used.

holate formation is preferably obtained by adding to a strong and concentrated alcohol, a suitable solid anhydrous metal hydroxide, such as sodium hydroxide with subsequent evaporation of excess alcohol. When proceeding in this manner, it is preferable to use an alcohol concentration of in excess of 90% and preferably in the aggregate of aliphatlc acid and rosin will The saponificatlon agent herein mentioned the dry saponification agent as such in the hydrofactory results. Care sh be taken, however. i that the entire amount of ree alcohol ultimately this alcohol content, the alcohol liberated from metal alcoholate containing crystal alcohol may sufilce as above pointed out for the cementation step in accordance with the invention. The amount of alcoholic be present or used for the cementatlon step in accordance with the invention dependsat least to some extent upon the particular alcohol. In most cases, however, .5 and preferably 1 to 1.5% of alcohol give satispresent in the solidified hydrocarbon product does not materially exceed about 3% calculated on the amount of hydrocarbon present. This is critical as alcohol contents appreciably in excess of 3% tend to deteriorate the qualities of the solidifled product, particularly by way of causing partial liquefaction thereof upon heating or burning. The amount of alcohol present in accordassasea ance with the invention, 1. e., not appreciably in excess of about 3% is at no time sufficient to interfere with the effective formation of insoluble soap gel and thus solidification of the hydrocarbon material. With amounts of 3% or less alcohol, however, no such liquefaction occurs.

The alcohol to be used for expediting the saponification reaction or bringing the same to the desired completion is preferably a primary aliphatic alcohol. The amount of this alcohol to be used may vary with the particular alcohol and depends, inter alia, upon considerations of solubility. I prefer to use methyl or ethyl alcohol. In most cases from 0.5 to 1.5% of added alcohol will bring the saponification reaction to the point of desired gel formation. If alcohol is used as a reaction booster and it is desired to add additional alcohol, when proceeding in accordance with the invention, care should be taken as afore set forth thatthe total amount of alcohol present in the ultimate product does not appreciably exceed 3% of the hydrocarbon present. I

The products obtained in accordance with the invention are substantially homogeneous and firm, can be cut with a knife, and handled as ordinary solids. The products will not liquefy when subject to raised temperatures and will burn without melting. The liquid material which they contain may be recovered in substantially unadulterated form by the application of pressure, centrifugal manipulations, distillation, or the like. Alternatively, the normally liquid material contained in the products in accordance with the invention in solidified form may be recovered by separation with the aid of suitable solvent extraction. In such case the extracting In the preparation of solidified products as hereinabove set forth, the particular organic compound or acid used in the saponification reaction may sometimes yield a product of a more or less heavy viscous molasses-like structure. This condition may be for instance encountered when using oleic acid. Though the resulting products are satisfactory for most purposes and will 'not meltwhen heated but on the contrary will become increasingly more solid, it is as a general rule particularly for shipping and handling purposes desirable to obtain greater solidity of the compound. In most cases the lack in desired solidity can be remedied by using the particular organic compound or acid in question together with an organic compound or acid of the type yielding solidified products of a high degree of solidity. By a proper proportioning of such organic or acid mixture, any desired intermediate solidity can be procured. For example where oleic acid is to be used in the saponificatlon reaction it is preferred to use a mixture of oleic acid with stearic acid or rosin.

The foregoing description is furnished by way of illustration and not of limitation and it is, therefore, my intention that the invention be limited only by the appended claims or their equiv- 1 alents wherein I have endeavored to claim broadsolvent is preferably one in which the metallic soap is preferentially soluble and in which the hydrocarbon in the solidified product is but limitedly soluble or substantially insoluble. In most instances the latter type recovery of liquid material may be procured by slushing the solidified product in accordance with the invention with water. p The products in accordance with the invention are characterized by a considerable density and represent essentially a substantially solid system predominantly containing alcohol, the hydrocarbon and the metallic soap. The solidified products are substantially free from voids and have a bulk specific gravity, i. e., specific gravity of the entire product, to at least the specific gravity of the normally liquid hydrocarbon component and preferably a bulk specific gravity approximately equivalent to the total weight of the components divided by the total volume of the components. By reason of their density and characteristics of structure the solidified products contair'iiegigligh volume percentage of normally liquid ma ly all inherent novelty.

I claim: 7

1. Method of making a substantially homogeneous solidified hydrocarbon product from a substantially granular non-homogeneous solidified hydrocarbon material which comprises heatin such hydrocarbon material without substantial removal of hydrocarbon, said hydrocarbon material containing ;as solidificant a voluminous soap gel, beinfiat least one member selected from the group consisting of higher aliphatic acid soaps and rosin soaps and non-melting when burning. and permitting said hydrocarbon material to cool while quiescent in the presence of a relatively small amount of alcohol not appreciably exceeding 3% by weight of the hydrocarbon presept without substantial amounts of alcohol bein .removed during cooling.

2. Method in accordance with claim 1 in which said hydrocarbon material is heated and per-.

- of methyl alcohol and ethyl alcohol.

ALBERT JOSEPH panama-E. 

